Tailoring Defects in B, N-Codoped Carbon Nanowalls for Direct Electrochemical Oxidation of Glyphosate and its Metabolites.

Tailoring the defects in graphene and its related carbon allotropes has great potential to exploit their enhanced electrochemical properties for energy applications, environmental remediation, and sensing. Vertical graphene, also known as carbon nanowalls (CNWs), exhibits a large surface area, enhanced charge transfer capability, and high defect density, making it suitable for a wide range of emerging applications. However, precise control and tuning of the defect size, position, and density remain challenging; moreover, due to their characteristic labyrinthine morphology, conventional characterization techniques and widely accepted quality indicators fail or need to be reformulated. This study primarily focuses on examining the impact of boron heterodoping and argon plasma treatment on CNW structures, uncovering complex interplays between specific defect-induced three-dimensional nanostructures and electrochemical performance. Moreover, the study introduces the use of defect-rich CNWs as a label-free electrode for directly oxidizing glyphosate (GLY), a common herbicide, and its metabolites (sarcosine and aminomethylphosphonic acid) for the first time. Crucially, we discovered that the presence of specific boron bonds (BC and BN), coupled with the absence of Lewis-base functional groups such as pyridinic-N, is essential for the oxidation of these analytes. Notably, the D+D* second-order combinational Raman modes at ≈2570 cm-1 emerged as a reliable indicator of the analytes' affinity. Contrary to expectations, the electrochemically active surface area and the presence of oxygen-containing functional groups played a secondary role. Argon-plasma post-treatment was found to adversely affect both the morphology and surface chemistry of CNWs, leading to an increase in sp3-hybridized carbon, the introduction of oxygen, and alterations in the types of nitrogen functional groups. Simulations support that certain defects are functional for GLY rather than AMPA. Sarcosine oxidation is the least affected by defect type.

Electrocatalytic performance of oxygen-activated carbon fibre felt anodes mediating degradation mechanism of acetaminophen in aqueous environments.

Carbon felts are flexible and scalable, have high specific areas, and are highly conductive materials that fit the requirements for both anodes and cathodes in advanced electrocatalytic processes. Advanced oxidative modification processes (thermal, chemical, and plasma-chemical) were applied to carbon felt anodes to enhance their efficiency towards electro-oxidation. The modification of the porous anodes results in increased kinetics of acetaminophen degradation in aqueous environments. The utilised oxidation techniques deliver single-step, straightforward, eco-friendly, and stable physiochemical reformation of carbon felt surfaces. The modifications caused minor changes in both the specific surface area and total pore volume corresponding with the surface morphology. A pristine carbon felt electrode was capable of decomposing up to 70% of the acetaminophen in a 240 min electrolysis process, while the oxygen-plasma treated electrode achieved a removal yield of 99.9% estimated utilising HPLC-UV-Vis. Here, the electro-induced incineration kinetics of acetaminophen resulted in a rate constant of 1.54 h-1, with the second-best result of 0.59 h-1 after oxidation in 30% H2O2. The kinetics of acetaminophen removal was synergistically studied by spectroscopic and electrochemical techniques, revealing various reaction pathways attributed to the formation of intermediate compounds such as p-aminophenol and others. The enhancement of the electrochemical oxidation rates towards acetaminophen was attributed to the appearance of surface carbonyl species. Our results indicate that the best-performing plasma-chemical treated CFE follows a heterogeneous mechanism with only approx. 40% removal due to direct electro-oxidation. The degradation mechanism of acetaminophen at the treated carbon felt anodes was proposed based on the detected intermediate products. Estimation of the cost-effectiveness of removal processes, in terms of energy consumption, was also elaborated. Although the study was focussed on acetaminophen, the achieved results could be adapted to also process emerging, hazardous pollutant groups such as anti-inflammatory pharmaceuticals.

Low-coherence photonic method of electrochemical processes monitoring.

We present an advanced multimodality characterization platform for simultaneous optical and electrochemical measurements of ferrocyanides. Specifically, we combined a fiber-optic Fabry-Perot interferometer with a three-electrode electrochemical setup to demonstrate a proof-of-principle of this hybrid characterization approach, and obtained feasibility data in its monitoring of electrochemical reactions in a boron-doped diamond film deposited on a silica substrate. The film plays the dual role of being the working electrode in the electrochemical reaction, as well as affording the reflectivity to enable the optical interferometry measurements. Optical responses during the redox reactions of the electrochemical process are presented. This work proves that simultaneous opto-electrochemical measurements of liquids are possible.

Carbon nanoarchitectures as high-performance electrodes for the electrochemical oxidation of landfill leachate.

Nanomaterials and assemblies of the aforementioned into complex architectures constitute an opportunity to design efficient and selective solutions to widespread and emerging environmental issues. The limited disposal of organic matter in modern landfills generates extremely concentrated leachates characterised by high concentrations of refractory compounds. Conventional biochemical treatment methods are unsuitable, while advanced treatment, such coagulation, reverse osmosis and ultrafiltration can be very costly and generate additional waste. Electrochemical oxidation is an established technique to efficiently mineralise a plethora of recalcitrant pollutants, however the selectivity and efficiency of the process are strongly related to the anode material. For this reason, a nanoarchitectured carbon material has been designed and synthesised to improve the capability of the anode towards the adsorption and decomposition of pollutants. Instead of simple nanostructures, intelligently engineered nanomaterials can come in handy for more efficient advanced treatment techniques. In this study, a carbon nanoarchitecture comprising boron-doped vertically aligned graphene walls (BCNWs) were grown on a boron-doped diamond (BDD) interfacial layer. The results show how the peculiar maze-like morphology and the concurrence of different carbon hybridisations resulted in a higher current exchange density. The BDD performed better for the removal of NH4+ while the BCNW-only sample exhibited a faster deactivation. The BDD/BCNW nanoarchitecture resulted in an enhanced COD removal and a NH4+ removal similar to that of BDD, without the intermediate production of NO2- and NO3-.

Self-discharge of electrochemical double layer capacitors.

Spontaneous voltage drop between EDLC electrodes, when it is kept under the open-circuit condition, is commonly called 'self-discharge' and is interpreted as a result of energy loss by the device. Three mechanisms of self-discharge were proposed: due to a leakage-current, faradaic reactions and charge redistribution. According to the law of energy preservation, if the voltage drop is associated with the energy loss, the energy would more likely be exchanged with the environment. While heat generation was measured during EDLC charging and discharging, the corresponding effect during storage under open-circuit conditions has not been reported. This may support the conclusion that voltage changes during 'self-discharge' are not related to a considerable energy loss. Moreover, it has been shown that a two-stage charging process, i.e. first galvanostatic charging followed by a potentiostatic charge redistribution, resulted in considerably slower potential changes when the device was switched to the open circuit. All discussed models were based on the assumption that the energy accumulated by EDLCs is proportional to the voltage in the second power, with capacitance (C/2) as the proportionality constant. However, it has been shown that during EDLC charging or discharging through a resistance R, equations valid for 'dielectric' and electrolytic capacitors, do not hold in the case of EDLCs. Consequently, the assumption that the energetic state of the EDLC is proportional at any time to the voltage in the second power may not be valid due to considerable variability of the 'constant' C. Therefore, voltage changes may not reflect the energetic state of the device.